Solid solution-strengthened copper alloys have the advantages of a simple composition and manufacturing process,high mechanical and electrical comprehensive performances,and low cost;thus,they are widely used in high-...Solid solution-strengthened copper alloys have the advantages of a simple composition and manufacturing process,high mechanical and electrical comprehensive performances,and low cost;thus,they are widely used in high-speed rail contact wires,electronic component connectors,and other devices.Overcoming the contradiction between low alloying and high performance is an important challenge in the development of solid solution-strengthened copper alloys.Taking the typical solid solution-strengthened alloy Cu-4Zn-1Sn as the research object,we proposed using the element In to replace Zn and Sn to achieve low alloying in this work.Two new alloys,Cu-1.5Zn-1Sn-0.4In and Cu-1.5Zn-0.9Sn-0.6In,were designed and prepared.The total weight percentage content of alloying elements decreased by 43%and 41%,respectively,while the product of ultimate tensile strength(UTS)and electrical conductivity(EC)of the annealed state increased by 14%and 15%.After cold rolling with a 90%reduction,the UTS of the two new alloys reached 576 and 627MPa,respectively,the EC was 44.9%IACS and 42.0%IACS,and the product of UTS and EC(UTS×EC)was 97%and 99%higher than that of the annealed state alloy.The dislocations proliferated greatly in cold-rolled alloys,and the strengthening effects of dislocations reached 332 and 356 MPa,respectively,which is the main reason for the considerable improvement in mechanical properties.展开更多
NiMZn/C@melamine sponge-derived carbon(MSDC)composites(M=Co,Fe,and Mn)were prepared by a vacuum pump-ing solution method followed by carbonization.A large number of carbon nanotubes(CNTs)homogeneously attached to the ...NiMZn/C@melamine sponge-derived carbon(MSDC)composites(M=Co,Fe,and Mn)were prepared by a vacuum pump-ing solution method followed by carbonization.A large number of carbon nanotubes(CNTs)homogeneously attached to the surfaces of the three-dimensional cross-linked of the sponge-derived carbon in the NiCoZn/C@MSDC composite,and CNTs were detected in the NiFeZn/C@MSDC and NiMnZn/C@MSDC composites.Ni_(3)ZnC_(0.7),Ni_(3)Fe,and MnO in-situ formed in the NiFeZn/C@MSDC and NiMnZn/C@MSDC composites.The CNTs in the NiCoZn/C@MSDC composite efficiently modulated its complex permittivity.Thus,the composite exhibited the best performance among the composites,with the minimum reflection loss(RL_(min))of-33.1 dB at 18 GHz and thickness of 1.4 mm.The bandwidth for RL of≤-10 dB was up to 5.04 GHz at the thickness of 1.7 mm and loading of 25wt%.The op-timized impedance matching,enhanced interfacial and dipole polarization,remarkable conduction loss,and multiple reflections and scat-tering of the incident microwaves improved the microwave absorption performance.The effects of Co,Ni,and Fe on the phase and mor-phology provided an alternative way for developing highly efficient and broadband microwave absorbers.展开更多
A series of La0.7-xSmxSr0.3MnO3, La0.7-xGdxSr0.3MnO3, and La0.7-xDyxSr0.3MnO3 (x=0.00, 0.10, 0.20, 0.30) samples were prepared by the solid-state reaction method. The influence of the substitution of Sm, Gd, and Dy ...A series of La0.7-xSmxSr0.3MnO3, La0.7-xGdxSr0.3MnO3, and La0.7-xDyxSr0.3MnO3 (x=0.00, 0.10, 0.20, 0.30) samples were prepared by the solid-state reaction method. The influence of the substitution of Sm, Gd, and Dy for La on the magnetic and electric properties and on the magnetoresistance (MR) was studied through measurements of M-T curves and p-T curves. The results showed that: lattice distortion induced by substitution of Sm, Gd, and Dy for La and extra magnetism of substitution had great influence on the magnetic and electric properties of pcrovskite manganites; substitution of magnetic rare earth element for La was an effective way to change Curie temperature and to strengthen MR in perovskite manganites; and appropriate substitution proportion would generate large MR near room temperature.展开更多
This paper reviews recent research on ductility improvement of B-undoped Ni_3Al alloys.Ni_3Al binary alloys with hypostoichiometric compositions show appreciable ductility at room temperature when the samples are prep...This paper reviews recent research on ductility improvement of B-undoped Ni_3Al alloys.Ni_3Al binary alloys with hypostoichiometric compositions show appreciable ductility at room temperature when the samples are prepared by recrystallization annealing after cold pressing,although the alloys with stoichiometric and hyperstoichiometric compositions remain brittle.Melt-spun ribbons with hypostoichiometric compositions contain fine anti-phase domains (APDs),while no APD can be seen in melt-spun ribbons with a hyperstoichiometric composition.The ductility in hypostoichiometric Ni_3Al alloys is associated with low ordering energy of the alloys.The addition of ternary elements,which have been classified as γ formers such as Pd,Pt,Cu,Co and Ag.improves ductility of Ni_3Al alloys.Correspondingly,the microstructure of the melt-spun ribbons consists of fine APDs.The addition of γ' formers such as Si,Ti,Zr,V,Nb and Ta leads to brittle intergranular frac- ture.No APD was observed in the melt-spun ribbons of these ternary alloys.展开更多
A systematic investigation of oxidation on a superconductive Fe Te_(0.5)Se_(0.5)thin film,which was grown on Nb-doped SrTiO_3(001) by pulsed laser deposition,has been carried out.The sample was exposed to ambien...A systematic investigation of oxidation on a superconductive Fe Te_(0.5)Se_(0.5)thin film,which was grown on Nb-doped SrTiO_3(001) by pulsed laser deposition,has been carried out.The sample was exposed to ambient air for one month for oxidation.Macroscopically,the exposed specimen lost its superconductivity due to oxidation.The specimen was subjected to in situ synchrotron radiation photoelectron spectroscopy(PES) and x-ray absorption spectroscopy(XAS) measurements following cycles of annealing and argon ion etching treatments to unravel what happened in the electronic structure and composition after exposure to air.By the spectroscopic measurements,we found that the as-grown FeTe_(0.5)Se_(0.5)superconductive thin film experienced an element selective substitution reaction.The oxidation preferentially proceeds through pumping out the Te and forming Fe–O bonds by O substitution of Te.In addition,our results certify that in situ vacuum annealing and low-energy argon ion etching methods combined with spectroscopy are suitable for depth element and valence analysis of layered structure superconductor materials.展开更多
The as-cast Mg2Ni-type Mg20–xYxNi10 (x=0, 1, 2, 3 and 4) electrode alloys were prepared by vacuum induction melting. Subsequently, the as-cast alloys were mechanically milled in a planetary-type ball mill. The analys...The as-cast Mg2Ni-type Mg20–xYxNi10 (x=0, 1, 2, 3 and 4) electrode alloys were prepared by vacuum induction melting. Subsequently, the as-cast alloys were mechanically milled in a planetary-type ball mill. The analyses of scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) reveal that nanocrystalline and amorphous structure can be obtained by mechanical milling, and the amount of amorphous phase increases with milling time prolonging. The electrochemical measurements show that the discharge capacity of Y0 alloy increases with milling time prolonging, while that of the Y-substituted alloys has a maximum value in the same condition. The cycle stabilities of the alloys decrease with milling time prolonging. The effect of milling time on the electrochemical kinetics of the alloys is related to Y content. Whenx=0, the high rate discharge ability, diffusion coefficient of hydrogen atom, limiting current density and charge transfer rate all increase with milling time prolonging, but the results are exactly opposite whenx=3.展开更多
The partial substitution of M (M=Sm, Nd, Pr) for La was performed in order to ameliorate the electrochemical hydrogen storage performance of RE–Mg–Ni-based A2B7-type electrode alloys. The La0.8–xMxMg0.2Ni3.35Al0....The partial substitution of M (M=Sm, Nd, Pr) for La was performed in order to ameliorate the electrochemical hydrogen storage performance of RE–Mg–Ni-based A2B7-type electrode alloys. The La0.8–xMxMg0.2Ni3.35Al0.1Si0.05 (M=Sm, Nd, Pr;x=0-0.4) electrode alloys were fabricated by casting and annealing and their microstructures were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The major phases (La, Mg)2Ni7 with the hexagonal Ce2Ni7-type structure and LaNi5 with the hexagonal CaCu5-type structure make up the basic microstructure of the experimental alloys. The discharge capacities of the as-cast and annealed alloys all gain their maximum values with the M (M=Sm, Nd, Pr) content varying. The electrochemical cycle stability of the as-cast and annealed alloys clearly rises with the M (M=Sm, Nd, Pr) content growing. Furthermore, the electrochemical kinetics of the alloys, including the high rate discharge ability, charge transfer rate, limiting current density and hydrogen diffusion coefficient, all present a increase trend at first and then decrease with the rising of M (M=Sm, Nd, Pr) content.展开更多
In order to improve the discharge capacity and cyclic life of Mg-Co-based alloy, ternary Mg45M5Co50 (M=Pd, Zr) alloys were synthesized via mechanical alloying. TEM analysis demonstrates that these alloys all possess...In order to improve the discharge capacity and cyclic life of Mg-Co-based alloy, ternary Mg45M5Co50 (M=Pd, Zr) alloys were synthesized via mechanical alloying. TEM analysis demonstrates that these alloys all possess body-centered cubic (BCC) phase in nano-crystalline. Electrochemical experiments show that Mg45Zr5Co50 electrode exhibits the highest capacity (425 mA·h/g) among the Mg45M5Co50 (M=Mg, Pd, Zr) alloys. And Mg45Pd5Co50 electrode lifts not only the initial discharge capacity (379 mA·h/g), but also the discharge kinetics, e.g., exchange current density and hydrogen diffusion ability from that of Mg50Co50. It could be concluded that the electrochemical performances were enhanced by substituting Zr and Pd for Mg in Mg-Co-based alloy.展开更多
In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology ...In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology was used to fabricate the La_(0.75-x)M_xMg_0.25Ni_3.2Co_0.2Al_0.1 (M = Zr, Pr; x = 0, 0.1) electrode alloys. The influences of the melt spinning and substituting La with M (M = Zr, Pr) on the structures and the electrochemical hydrogen storage characteristics of the alloys were investigated. The analysis of XRD, SEM, and TEM reveals that the as-cast and spun alloys have a multiphase structure composed of two main phases (La, Mg)_2Ni_7 and LaNi_5 as well as a residual phase LaNi_2 . The as-spun (M = Pr) alloy displays an entire nanocrystalline structure, while an amorphous-like structure is detected in the as-spun (M = Zr) alloy, implying that the substitution of Zr for La facilitates the amorphous formation. The electrochemical measurements exhibit that the substitution of Pr for La clearly increases the discharge capacity of the alloys; however, the Zr substitution brings on an adverse impact. Meanwhile, the M (M = Zr, Pr) substitution significantly enhances its cycle stability. The melt spinning exerts an evident effect on the electrochemical performances of the alloys, whose discharge capacity and high rate discharge ability (HRD) first mount up and then fall with the growing spinning rate, whereas their cycle stabilities monotonously augment as the spinning rate increases.展开更多
In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4...In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4)alloys prepared by melt spinning has been carried out.The analysis of XRD and TEM reveals that the as-spun(M=None,Cu)alloys display an entire nanocrystalline structure,whereas the as-spun(M=Co,Mn)alloys hold a mixed structure of nanocrystalline and amorphous structure when M content x=4,indicating that the substitution of M(M=Co,Mn)for Ni facilitates the glass formation in the Mg2Ni-type alloy.Besides,all the as-spun alloys have a major phase of Mg2Ni but M(M=Co,Mn)substitution brings on the formation of some secondary phases,MgCo2 and Mg phases for M=Co as well as MnNi and Mg phases for M=Mn.Based upon the measurements of the automatic Sieverts apparatus and the automatic galvanostatic system,the impacts engendered by M(M=Cu,Co,Mn)substitution on the gaseous and electrochemical hydrogen storage kinetics of the alloys appear to be evident.The gaseous hydriding kinetics of the alloys first rises and then declines with the growing of M(M=Cu,Co,Mn)content.Particularly,the M(M= Mn)substitution results in a sharp drop in the hydriding kinetics when x=4.The M(M=Cu,Co,Mn)substitution ameliorates the dehydriding kinetics dramatically in the order(M=Co)>(M=Mn)>(M=Cu).The electrochemical kinetics of the alloys visibly grows with M content rising for(M=Cu,Co),while it first increases and then declines for(M=Mn).展开更多
In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La...In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Cu, Al, Mn; x=0, 0.1) were prepared by casting and rapid quenching. The effects of element substitution and rapid quenching on the microstructures and electrochemical performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys have a multiphase structure, including the (La, Mg)Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. The rapid quenching significantly improves the composition homogeneity of the alloys and markedly decreases the grain size of the alloys. The Cu substitution promotes the formation of an amorphous phase in the as-quenched alloy, and a reversal result by the Al substitution. The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, whereas it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al>Cu>Mn, and negative influence on the discharge capacity is in sequence Al>Mn>Cu. The rapid quenching significantly enhances the cycle stability of the alloys, but it leads to a different extent decrease of the discharge capacity of the alloys.展开更多
We focus on the electrochemical dissolution characteristics of new titanium alloys such as near-αtitanium alloy Ti60,α+βtitanium alloy TC4andβtitanium alloy Ti40 which are often used for aerospace industry.The exp...We focus on the electrochemical dissolution characteristics of new titanium alloys such as near-αtitanium alloy Ti60,α+βtitanium alloy TC4andβtitanium alloy Ti40 which are often used for aerospace industry.The experiments are carried out by electrochemical machining tool,and the surface morphology of the specimens is observed by the scanning electron microscope(SEM)and three-dimensional video microscope(DVM).The appropriate electrolyte is selected and the relationships between surface roughness and current density are achieved.The results show that the single-phase titanium alloy Ti40 has a better surface roughness after ECM compared with theα+βtitanium alloy TC4 and the near-αtitanium alloy Ti60.The best surface roughness is Ra 0.28μm when the current density is 75A/cm2.Furthermore,the surface roughness of the near-αtitanium alloy Ti60 is the most sensitive with the current density because of the different electrochemical equivalents of substitutional elements and larger grains than TC4.Finally,the suitable current density for each titanium alloy is achieved.展开更多
La-Mg-Ni system (PuNi3-type) hydrogen storage alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Fe, Cu, Al; x=0, 0.1) were prepared by casting and rapid quenching. Aiming to improve the cycle stabilities of the alloys, Ni in the a...La-Mg-Ni system (PuNi3-type) hydrogen storage alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Fe, Cu, Al; x=0, 0.1) were prepared by casting and rapid quenching. Aiming to improve the cycle stabilities of the alloys, Ni in the alloy was partly substituted by Fe, Cu and Al. The effects of the substitution of Fe, Cu and Al for Ni and the rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that the element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Cu obviously increases the amount of the LaNi2 phase. The substitution of Al and Fe leads to a great refinement of the as-quenched alloy′s grains. The substitution of Al strongly restrains the formation of the amorphous in the as-quenched alloy, but the substitution of Fe and Cu is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Cu and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive impact of the substitution elements on the cycle stabilities of the as-cast alloys is ranked in proper order Al>Fe>Cu, and for as-quenched alloys, the order is Fe>Al>Cu. Rapid quenching engenders an unconscious influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.展开更多
Bi- and Cu-substituted Ca3Co4O9 samples were prepared by conventional solid-state reaction method and the effect of element substitution on the microstructures and thermoelectric properties was investigated. Partial s...Bi- and Cu-substituted Ca3Co4O9 samples were prepared by conventional solid-state reaction method and the effect of element substitution on the microstructures and thermoelectric properties was investigated. Partial substitution of Cu for Co leads to an increase in electrical conductivity and a decrease in Seebeck coefficient due to the rise of hole concentration. The microstructure of Cu-substituted sample is almost unchanged compared with undoped Ca3Co4O9. On the other hand, partial substitution of Bi for Ca gives rise to a significant increase in the grain size, and c-axis-oriented structure can be formed in Ca2.7Bi0.3Co4O9, resulting in an obvious increase in electrical conductivity. Cu and Bi co-substitution further increases the grain growth and the electrical conductivity of Ca2.7Bi0.3Co3.7Cu0.3O9. Thus, Cu and Bi co-substitution samples possess the optimal thermoelectric performance at high temperature and the highest value of power factor can reach 3.1×10^-4 Wm^-1.K^-2 at 1000 K.展开更多
In this paper, the mathematical and physical model was developed based on thermodynamics and solidification theory before the eutectoid transformation of nodular graphite iron occurred. The Local Element Substitute an...In this paper, the mathematical and physical model was developed based on thermodynamics and solidification theory before the eutectoid transformation of nodular graphite iron occurred. The Local Element Substitute and Magnification Method was brought forward and 3-dimensional numerical simulation program based on the model and the new assistant algorithm was developed and used to calculate the samples. Results of calculation have good agreement with experimental data. To display the microstructure formation during solidification of nodular graphite iron, a 2-dimensional numerical simulation program combined with the result of the 3-dimensional numerical simulation of experimental samples was compiled.展开更多
The approach of substituting electrochemically active with inactive elements has widely been used to improve the electrochemical performance of Li-rich intercalation cathode materials. This especially is true for Li-r...The approach of substituting electrochemically active with inactive elements has widely been used to improve the electrochemical performance of Li-rich intercalation cathode materials. This especially is true for Li-rich compounds where almost all of the Li+ions are reversibly(de)intercalated during electrochemical cycling. The beneficial mechanism behind this substitution with electrochemically inactive elements is still not clear yet. Li_(2)RuO_(3) is chosen as basis for a model solid solution system to investigate the effect of electrochemically inactive elements owing to its high specific capacity of more than 300 m Ah g^(-1) and the significant contribution of anion redox mechanism. Herein, Li_(2)Ru_(1-x)Ti_xO_(3) solid solution series are synthesized and the effect of substituting with electrochemical inactive Ti for Ru on structure and electrochemical performance have been comprehensively investigated. The electrochemical performance is significantly improved, especially for Li_(2)Ru_(0.8)Ti_(0.2)O_(3), and the capacity retention after 50 cycles increases from 81% to 90%, as compared to the end member Li_(2)RuO_(3). Results of electrochemical impedance spectroscopy show that Ti substitution reduces the charge transfer impedance, which favors the Li+diffusion across the electrolyte–electrode interface and improves the electronic conductivity. For the first time,nuclear magnetic resonance was utilized to confirm that a small part of Ti ions exchange their position with Li ions in the Li layer. This research provides a better understanding of electrochemical inactive element substitution and strong insights for the functional design of the next generation of Li-rich cathode materials.展开更多
We report the structural and electrical transport properties of Fe1-xCuxSe(x=0,0.02,0.05,0.10)single crystals grown by a chemical vapor transport method.Substituting Cu for Fe suppresses both the nematicity and superc...We report the structural and electrical transport properties of Fe1-xCuxSe(x=0,0.02,0.05,0.10)single crystals grown by a chemical vapor transport method.Substituting Cu for Fe suppresses both the nematicity and superconductivity of FeSe single crystal,and provokes a metal–insulator transition.Our Hall measurements show that the Cu substitution also changes an electron dominance at low temperature of un-doped Fe Se to a hole dominance of Cu-doped Fe1-xCuxSe at x=0.02 and 0.1,and reduces the sign-change temperature(TR)of the Hall coefficient(RH).展开更多
In the framework of density functional theory (DFT), the electronic excitations and nonlinear optical (NLO) properties of six binuclear transition metal cluster anions with the formula of [Ch2M-(μ-Ch)2-M'CN]^...In the framework of density functional theory (DFT), the electronic excitations and nonlinear optical (NLO) properties of six binuclear transition metal cluster anions with the formula of [Ch2M-(μ-Ch)2-M'CN]^2- (M = Mo, W; Ch = S, Se; M' = Cu, Ag) have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M'→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M'CN as well as those of μ-Ch→M and M'→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M'CN make larger contributions to the hyperpolarizability, especially to γ.展开更多
Proton conducting solid oxide fuel cell(H-SOFC)is an emerging energy conversion device,with lower activation energy and higher energy utilization efficiency.However,the deficiency of highly active cathode materials st...Proton conducting solid oxide fuel cell(H-SOFC)is an emerging energy conversion device,with lower activation energy and higher energy utilization efficiency.However,the deficiency of highly active cathode materials still remains a major challenge for the development of H-SOFC.Therefore,in this work,K_(2)NiF_(4)-type cathode materials Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ)(x=0,0.1,0.2,0.3),single-phase tripleconducting(e-/O^(2-)/H^(+))oxides,are prepared for intermediate temperature H-SOFCs and exhibit good oxygen reduction reaction activity.The investigation demonstrates that doping Ba into Pr_(2-x)BaxNi_(0.6)Cu_(0.4)O_(4+δ) can increase its electrochemical performance through enhancing electrical conductivity,oxygen vacancy concentration and proton conductivity.EIS tests are carried at 750℃ and the minimum polarization impedances are obtained when x=0.2,which are 0.068 Ω·cm^(2) in air and 1.336 Ω·cm^(2) in wet argon,respectively.The peak power density of the cell with Pr_(1.8)Ba_(0.2)Ni_(0.6)Cu_(0.4)O_(4+δ) cathode is 298 mW·cm^(-2) at 750℃ in air with humidified hydrogen as fuel.Based on the above results,Ba-doped Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ) can be a good candidate material for SOFC cathode applications.展开更多
The element Ni in the Mg2Ni alloy is partially substituted by M(M = Cu, Co, Mn) in order to ameliorate the electrochemical hydrogen storage performances of Mg2Ni-type electrode alloys. The nanocrystalline and amorph...The element Ni in the Mg2Ni alloy is partially substituted by M(M = Cu, Co, Mn) in order to ameliorate the electrochemical hydrogen storage performances of Mg2Ni-type electrode alloys. The nanocrystalline and amorphous Mg20Ni10-xMx(M = None, Cu, Co, Mn; x = 0-4) alloys were prepared by melt spinning. The effects of the M(M = Cu, Co, Mn) content on the structures and electrochemical hydrogen storage characteristics of the as-cast and spun alloys were comparatively studied. The analyses by XRD, SEM and HRTEM reveal that all the as-cast alloys have a major phase of Mg2Ni but the M(M = Co, Mn) substitution brings on the formation of some secondary phases, MgCo2 and Mg for the(M = Co) alloy, and Mn Ni and Mg for the(M = Mn) alloy. Besides, the as-spun(M = None, Cu) alloys display an entirely nanocrystalline structure, whereas the as-spun(M = Co, Mn) alloys hold a nanocrystalline/amorphous structure, suggesting that the substitution of M(M = Co, Mn) for Ni facilitates the glass formation in the Mg2Ni-type alloys. The electrochemical measurements indicate that the variation of M(M = Cu, Co, Mn) content engenders an obvious effect on the electrochemical performances of the as-cast and spun alloys. To be specific, the cyclic stabilities of the alloys augment monotonously with increasing M(M = Cu, Co, Mn) content, and the capacity retaining rate(S20) is in an order of(M = Cu) 〉(M = Co) 〉(M = Mn) 〉(M = None) for x≤1 but changes to(M = Co) 〉(M = Mn) 〉(M = Cu) 〉(M = None) for x≥2. The discharge capacities of the as-cast and spun alloys always grow with the rising of M(M = Co, Mn) content but first mount up and then go down with increasing M(M = Cu) content. Whatever the M content is, the discharge capacities are in sequence:(M = Co) 〉(M = Mn) 〉(M = Cu) 〉(M = None). The high rate discharge abilities(HRDs) of all the alloys grow clearly with rising M(M = Cu, Co) content except for(M = Mn) alloy, whose HRD has a maximum value with varying M(M = Mn) content. Furthermore, for the as-cast alloys, the HRD is in order of(M = Co) 〉(M = Mn) 〉(M = Cu) 〉(M = None), while for the as-spun(20 m·s^-1) alloys, it changes from(M = Co) 〉(M = Mn) 〉(M = Cu) 〉(M = None) for x = 1 to(M = Cu) 〉(M = Co) 〉(M = None) 〉(M = Mn) for x = 4.展开更多
基金financially supported by the National Key Research and Development Program of China(No.2021YFB3803101)the National Natural Science Foundation of China(Nos.52022011,51974028,and 52090041)+1 种基金the Xiaomi Young Scholars ProgramChina National Postdoctoral Program for Innovative Talents(No.BX20230042)。
文摘Solid solution-strengthened copper alloys have the advantages of a simple composition and manufacturing process,high mechanical and electrical comprehensive performances,and low cost;thus,they are widely used in high-speed rail contact wires,electronic component connectors,and other devices.Overcoming the contradiction between low alloying and high performance is an important challenge in the development of solid solution-strengthened copper alloys.Taking the typical solid solution-strengthened alloy Cu-4Zn-1Sn as the research object,we proposed using the element In to replace Zn and Sn to achieve low alloying in this work.Two new alloys,Cu-1.5Zn-1Sn-0.4In and Cu-1.5Zn-0.9Sn-0.6In,were designed and prepared.The total weight percentage content of alloying elements decreased by 43%and 41%,respectively,while the product of ultimate tensile strength(UTS)and electrical conductivity(EC)of the annealed state increased by 14%and 15%.After cold rolling with a 90%reduction,the UTS of the two new alloys reached 576 and 627MPa,respectively,the EC was 44.9%IACS and 42.0%IACS,and the product of UTS and EC(UTS×EC)was 97%and 99%higher than that of the annealed state alloy.The dislocations proliferated greatly in cold-rolled alloys,and the strengthening effects of dislocations reached 332 and 356 MPa,respectively,which is the main reason for the considerable improvement in mechanical properties.
基金supported by research pro-grams of National Natural Science Foundation of China(Nos.52101274 and 52377026)Natural Science Foundation of Shandong Province,China(Nos.ZR2020QE011 and ZR2022ME089)+4 种基金Taishan Scholars and Young Experts Pro-gram of Shandong Province,China(No.tsqn202103057)the Qingchuang Talents Induction Program of Shandong Higher Education Institution,China(Research and Innovation Team of Structural-Functional Polymer Composites)Special Fin-ancial of Shandong Province,China(Structural Design of High-efficiency Electromagnetic Wave-absorbing Composite Materials and Construction of Shandong Provincial Talent Teams),Youth Top Talent Foundation of Yantai University(No.2219008)Graduate Innovation Foundation of Yantai University(No.GIFYTU2240)College Student Innovation and Entrepreneurship Training Program Project(No.202311066088).
文摘NiMZn/C@melamine sponge-derived carbon(MSDC)composites(M=Co,Fe,and Mn)were prepared by a vacuum pump-ing solution method followed by carbonization.A large number of carbon nanotubes(CNTs)homogeneously attached to the surfaces of the three-dimensional cross-linked of the sponge-derived carbon in the NiCoZn/C@MSDC composite,and CNTs were detected in the NiFeZn/C@MSDC and NiMnZn/C@MSDC composites.Ni_(3)ZnC_(0.7),Ni_(3)Fe,and MnO in-situ formed in the NiFeZn/C@MSDC and NiMnZn/C@MSDC composites.The CNTs in the NiCoZn/C@MSDC composite efficiently modulated its complex permittivity.Thus,the composite exhibited the best performance among the composites,with the minimum reflection loss(RL_(min))of-33.1 dB at 18 GHz and thickness of 1.4 mm.The bandwidth for RL of≤-10 dB was up to 5.04 GHz at the thickness of 1.7 mm and loading of 25wt%.The op-timized impedance matching,enhanced interfacial and dipole polarization,remarkable conduction loss,and multiple reflections and scat-tering of the incident microwaves improved the microwave absorption performance.The effects of Co,Ni,and Fe on the phase and mor-phology provided an alternative way for developing highly efficient and broadband microwave absorbers.
基金supported by the Key Programme of the National Natural Science Foundation of China (19934003)the Grand Programme of the Natu-ral Science Research of Education Bureau of Anhui Province (ZD2007003-1)+1 种基金 Natural Science Research Programme of Colleges and Universi-ties of Anhui Province (KJ2008A19ZC) Professors’ and Doctors’ Research Foundation of Suzhou College (2006jb02)
文摘A series of La0.7-xSmxSr0.3MnO3, La0.7-xGdxSr0.3MnO3, and La0.7-xDyxSr0.3MnO3 (x=0.00, 0.10, 0.20, 0.30) samples were prepared by the solid-state reaction method. The influence of the substitution of Sm, Gd, and Dy for La on the magnetic and electric properties and on the magnetoresistance (MR) was studied through measurements of M-T curves and p-T curves. The results showed that: lattice distortion induced by substitution of Sm, Gd, and Dy for La and extra magnetism of substitution had great influence on the magnetic and electric properties of pcrovskite manganites; substitution of magnetic rare earth element for La was an effective way to change Curie temperature and to strengthen MR in perovskite manganites; and appropriate substitution proportion would generate large MR near room temperature.
文摘This paper reviews recent research on ductility improvement of B-undoped Ni_3Al alloys.Ni_3Al binary alloys with hypostoichiometric compositions show appreciable ductility at room temperature when the samples are prepared by recrystallization annealing after cold pressing,although the alloys with stoichiometric and hyperstoichiometric compositions remain brittle.Melt-spun ribbons with hypostoichiometric compositions contain fine anti-phase domains (APDs),while no APD can be seen in melt-spun ribbons with a hyperstoichiometric composition.The ductility in hypostoichiometric Ni_3Al alloys is associated with low ordering energy of the alloys.The addition of ternary elements,which have been classified as γ formers such as Pd,Pt,Cu,Co and Ag.improves ductility of Ni_3Al alloys.Correspondingly,the microstructure of the melt-spun ribbons consists of fine APDs.The addition of γ' formers such as Si,Ti,Zr,V,Nb and Ta leads to brittle intergranular frac- ture.No APD was observed in the melt-spun ribbons of these ternary alloys.
基金Project supported by the Chinese Academy of Sciences(Grant No.1G2009312311750101)the National Natural Science Foundation of China(Grant Nos.11375228,11204303,and U1332105)
文摘A systematic investigation of oxidation on a superconductive Fe Te_(0.5)Se_(0.5)thin film,which was grown on Nb-doped SrTiO_3(001) by pulsed laser deposition,has been carried out.The sample was exposed to ambient air for one month for oxidation.Macroscopically,the exposed specimen lost its superconductivity due to oxidation.The specimen was subjected to in situ synchrotron radiation photoelectron spectroscopy(PES) and x-ray absorption spectroscopy(XAS) measurements following cycles of annealing and argon ion etching treatments to unravel what happened in the electronic structure and composition after exposure to air.By the spectroscopic measurements,we found that the as-grown FeTe_(0.5)Se_(0.5)superconductive thin film experienced an element selective substitution reaction.The oxidation preferentially proceeds through pumping out the Te and forming Fe–O bonds by O substitution of Te.In addition,our results certify that in situ vacuum annealing and low-energy argon ion etching methods combined with spectroscopy are suitable for depth element and valence analysis of layered structure superconductor materials.
基金Projects(51161015,51371094)supported by the National Natural Science Foundation of China
文摘The as-cast Mg2Ni-type Mg20–xYxNi10 (x=0, 1, 2, 3 and 4) electrode alloys were prepared by vacuum induction melting. Subsequently, the as-cast alloys were mechanically milled in a planetary-type ball mill. The analyses of scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) reveal that nanocrystalline and amorphous structure can be obtained by mechanical milling, and the amount of amorphous phase increases with milling time prolonging. The electrochemical measurements show that the discharge capacity of Y0 alloy increases with milling time prolonging, while that of the Y-substituted alloys has a maximum value in the same condition. The cycle stabilities of the alloys decrease with milling time prolonging. The effect of milling time on the electrochemical kinetics of the alloys is related to Y content. Whenx=0, the high rate discharge ability, diffusion coefficient of hydrogen atom, limiting current density and charge transfer rate all increase with milling time prolonging, but the results are exactly opposite whenx=3.
基金Projects(51161015,51371094)supported by the National Natural Science Foundations of China
文摘The partial substitution of M (M=Sm, Nd, Pr) for La was performed in order to ameliorate the electrochemical hydrogen storage performance of RE–Mg–Ni-based A2B7-type electrode alloys. The La0.8–xMxMg0.2Ni3.35Al0.1Si0.05 (M=Sm, Nd, Pr;x=0-0.4) electrode alloys were fabricated by casting and annealing and their microstructures were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The major phases (La, Mg)2Ni7 with the hexagonal Ce2Ni7-type structure and LaNi5 with the hexagonal CaCu5-type structure make up the basic microstructure of the experimental alloys. The discharge capacities of the as-cast and annealed alloys all gain their maximum values with the M (M=Sm, Nd, Pr) content varying. The electrochemical cycle stability of the as-cast and annealed alloys clearly rises with the M (M=Sm, Nd, Pr) content growing. Furthermore, the electrochemical kinetics of the alloys, including the high rate discharge ability, charge transfer rate, limiting current density and hydrogen diffusion coefficient, all present a increase trend at first and then decrease with the rising of M (M=Sm, Nd, Pr) content.
基金Projects(51471087,61370042,21173041,11204031,11472080)supported by the National Natural Science Foundation of ChinaProject(13KJA430003)supported by the Jiangsu Higher Education Institutions of ChinaProject(BK20141336)supported by the Natural Science Foundation of Jiangsu Province,China
文摘In order to improve the discharge capacity and cyclic life of Mg-Co-based alloy, ternary Mg45M5Co50 (M=Pd, Zr) alloys were synthesized via mechanical alloying. TEM analysis demonstrates that these alloys all possess body-centered cubic (BCC) phase in nano-crystalline. Electrochemical experiments show that Mg45Zr5Co50 electrode exhibits the highest capacity (425 mA·h/g) among the Mg45M5Co50 (M=Mg, Pd, Zr) alloys. And Mg45Pd5Co50 electrode lifts not only the initial discharge capacity (379 mA·h/g), but also the discharge kinetics, e.g., exchange current density and hydrogen diffusion ability from that of Mg50Co50. It could be concluded that the electrochemical performances were enhanced by substituting Zr and Pd for Mg in Mg-Co-based alloy.
基金supported by the National Natural Science Foundation of China(Nos.51161015 and 50961009)the National High-Technology Research and Development Program of China(No.2011AA03A408)the Natural Science Foundation of Inner Mongolia,China(Nos.2011ZD10 and 2010ZD05)
文摘In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology was used to fabricate the La_(0.75-x)M_xMg_0.25Ni_3.2Co_0.2Al_0.1 (M = Zr, Pr; x = 0, 0.1) electrode alloys. The influences of the melt spinning and substituting La with M (M = Zr, Pr) on the structures and the electrochemical hydrogen storage characteristics of the alloys were investigated. The analysis of XRD, SEM, and TEM reveals that the as-cast and spun alloys have a multiphase structure composed of two main phases (La, Mg)_2Ni_7 and LaNi_5 as well as a residual phase LaNi_2 . The as-spun (M = Pr) alloy displays an entire nanocrystalline structure, while an amorphous-like structure is detected in the as-spun (M = Zr) alloy, implying that the substitution of Zr for La facilitates the amorphous formation. The electrochemical measurements exhibit that the substitution of Pr for La clearly increases the discharge capacity of the alloys; however, the Zr substitution brings on an adverse impact. Meanwhile, the M (M = Zr, Pr) substitution significantly enhances its cycle stability. The melt spinning exerts an evident effect on the electrochemical performances of the alloys, whose discharge capacity and high rate discharge ability (HRD) first mount up and then fall with the growing spinning rate, whereas their cycle stabilities monotonously augment as the spinning rate increases.
基金Projects(51161015,51371094)supported by National Natural Science Foundations of ChinaProject(2011ZD10)supported by Natural Science Foundation of Inner Mongolia,China
文摘In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4)alloys prepared by melt spinning has been carried out.The analysis of XRD and TEM reveals that the as-spun(M=None,Cu)alloys display an entire nanocrystalline structure,whereas the as-spun(M=Co,Mn)alloys hold a mixed structure of nanocrystalline and amorphous structure when M content x=4,indicating that the substitution of M(M=Co,Mn)for Ni facilitates the glass formation in the Mg2Ni-type alloy.Besides,all the as-spun alloys have a major phase of Mg2Ni but M(M=Co,Mn)substitution brings on the formation of some secondary phases,MgCo2 and Mg phases for M=Co as well as MnNi and Mg phases for M=Mn.Based upon the measurements of the automatic Sieverts apparatus and the automatic galvanostatic system,the impacts engendered by M(M=Cu,Co,Mn)substitution on the gaseous and electrochemical hydrogen storage kinetics of the alloys appear to be evident.The gaseous hydriding kinetics of the alloys first rises and then declines with the growing of M(M=Cu,Co,Mn)content.Particularly,the M(M= Mn)substitution results in a sharp drop in the hydriding kinetics when x=4.The M(M=Cu,Co,Mn)substitution ameliorates the dehydriding kinetics dramatically in the order(M=Co)>(M=Mn)>(M=Cu).The electrochemical kinetics of the alloys visibly grows with M content rising for(M=Cu,Co),while it first increases and then declines for(M=Mn).
基金This work was financially supported by National Natural Science Foundation of China ( No.50131040)Science and Technology Planned Project of Inner Mongolia, China ( No.20050205)Higher Education Science Research Project ofInner Mongolia, China (No.NJ05064)
文摘In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Cu, Al, Mn; x=0, 0.1) were prepared by casting and rapid quenching. The effects of element substitution and rapid quenching on the microstructures and electrochemical performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys have a multiphase structure, including the (La, Mg)Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. The rapid quenching significantly improves the composition homogeneity of the alloys and markedly decreases the grain size of the alloys. The Cu substitution promotes the formation of an amorphous phase in the as-quenched alloy, and a reversal result by the Al substitution. The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, whereas it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al>Cu>Mn, and negative influence on the discharge capacity is in sequence Al>Mn>Cu. The rapid quenching significantly enhances the cycle stability of the alloys, but it leads to a different extent decrease of the discharge capacity of the alloys.
基金supported by the National Natural Science Foundation of China(No.51205199)the Program for New Century Excellent Talents in University (No.NCET12-0627)+1 种基金the Funding of Jiangsu Innovation Program for Graduate Education (No.CXLX13_141)the Fundamental Research Funds for the Central Universities
文摘We focus on the electrochemical dissolution characteristics of new titanium alloys such as near-αtitanium alloy Ti60,α+βtitanium alloy TC4andβtitanium alloy Ti40 which are often used for aerospace industry.The experiments are carried out by electrochemical machining tool,and the surface morphology of the specimens is observed by the scanning electron microscope(SEM)and three-dimensional video microscope(DVM).The appropriate electrolyte is selected and the relationships between surface roughness and current density are achieved.The results show that the single-phase titanium alloy Ti40 has a better surface roughness after ECM compared with theα+βtitanium alloy TC4 and the near-αtitanium alloy Ti60.The best surface roughness is Ra 0.28μm when the current density is 75A/cm2.Furthermore,the surface roughness of the near-αtitanium alloy Ti60 is the most sensitive with the current density because of the different electrochemical equivalents of substitutional elements and larger grains than TC4.Finally,the suitable current density for each titanium alloy is achieved.
基金National Natural Science Foundation of China (50642033)Key Technologies R&D Programof Inner Mongolia ,China (20050205)Higher Education Science Research Project of In-ner Mongolia ,China (NJ05064)
文摘La-Mg-Ni system (PuNi3-type) hydrogen storage alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Fe, Cu, Al; x=0, 0.1) were prepared by casting and rapid quenching. Aiming to improve the cycle stabilities of the alloys, Ni in the alloy was partly substituted by Fe, Cu and Al. The effects of the substitution of Fe, Cu and Al for Ni and the rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that the element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Cu obviously increases the amount of the LaNi2 phase. The substitution of Al and Fe leads to a great refinement of the as-quenched alloy′s grains. The substitution of Al strongly restrains the formation of the amorphous in the as-quenched alloy, but the substitution of Fe and Cu is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Cu and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive impact of the substitution elements on the cycle stabilities of the as-cast alloys is ranked in proper order Al>Fe>Cu, and for as-quenched alloys, the order is Fe>Al>Cu. Rapid quenching engenders an unconscious influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.
基金supported by the Foundation for University Key Teacher of Henan Province, China (2008136)Doctoral Fund of Henan Institute of Engineering(D2007011), China
文摘Bi- and Cu-substituted Ca3Co4O9 samples were prepared by conventional solid-state reaction method and the effect of element substitution on the microstructures and thermoelectric properties was investigated. Partial substitution of Cu for Co leads to an increase in electrical conductivity and a decrease in Seebeck coefficient due to the rise of hole concentration. The microstructure of Cu-substituted sample is almost unchanged compared with undoped Ca3Co4O9. On the other hand, partial substitution of Bi for Ca gives rise to a significant increase in the grain size, and c-axis-oriented structure can be formed in Ca2.7Bi0.3Co4O9, resulting in an obvious increase in electrical conductivity. Cu and Bi co-substitution further increases the grain growth and the electrical conductivity of Ca2.7Bi0.3Co3.7Cu0.3O9. Thus, Cu and Bi co-substitution samples possess the optimal thermoelectric performance at high temperature and the highest value of power factor can reach 3.1×10^-4 Wm^-1.K^-2 at 1000 K.
文摘In this paper, the mathematical and physical model was developed based on thermodynamics and solidification theory before the eutectoid transformation of nodular graphite iron occurred. The Local Element Substitute and Magnification Method was brought forward and 3-dimensional numerical simulation program based on the model and the new assistant algorithm was developed and used to calculate the samples. Results of calculation have good agreement with experimental data. To display the microstructure formation during solidification of nodular graphite iron, a 2-dimensional numerical simulation program combined with the result of the 3-dimensional numerical simulation of experimental samples was compiled.
基金supported by the Nature Science Foundation of Changchun Normal University and Research Foundation for Advanced Doctor of Changchun Normal University。
文摘The approach of substituting electrochemically active with inactive elements has widely been used to improve the electrochemical performance of Li-rich intercalation cathode materials. This especially is true for Li-rich compounds where almost all of the Li+ions are reversibly(de)intercalated during electrochemical cycling. The beneficial mechanism behind this substitution with electrochemically inactive elements is still not clear yet. Li_(2)RuO_(3) is chosen as basis for a model solid solution system to investigate the effect of electrochemically inactive elements owing to its high specific capacity of more than 300 m Ah g^(-1) and the significant contribution of anion redox mechanism. Herein, Li_(2)Ru_(1-x)Ti_xO_(3) solid solution series are synthesized and the effect of substituting with electrochemical inactive Ti for Ru on structure and electrochemical performance have been comprehensively investigated. The electrochemical performance is significantly improved, especially for Li_(2)Ru_(0.8)Ti_(0.2)O_(3), and the capacity retention after 50 cycles increases from 81% to 90%, as compared to the end member Li_(2)RuO_(3). Results of electrochemical impedance spectroscopy show that Ti substitution reduces the charge transfer impedance, which favors the Li+diffusion across the electrolyte–electrode interface and improves the electronic conductivity. For the first time,nuclear magnetic resonance was utilized to confirm that a small part of Ti ions exchange their position with Li ions in the Li layer. This research provides a better understanding of electrochemical inactive element substitution and strong insights for the functional design of the next generation of Li-rich cathode materials.
基金Project supported by the National Key Research and Development of China(Grant No.2018YFA0704200)the National Natural Science Foundation of China(Grant No.11834016)the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB25000000)。
文摘We report the structural and electrical transport properties of Fe1-xCuxSe(x=0,0.02,0.05,0.10)single crystals grown by a chemical vapor transport method.Substituting Cu for Fe suppresses both the nematicity and superconductivity of FeSe single crystal,and provokes a metal–insulator transition.Our Hall measurements show that the Cu substitution also changes an electron dominance at low temperature of un-doped Fe Se to a hole dominance of Cu-doped Fe1-xCuxSe at x=0.02 and 0.1,and reduces the sign-change temperature(TR)of the Hall coefficient(RH).
基金the National Natural Science Foundation of China (No. 20573114)Foundation of Fujian Province (No. 2006F3133)
文摘In the framework of density functional theory (DFT), the electronic excitations and nonlinear optical (NLO) properties of six binuclear transition metal cluster anions with the formula of [Ch2M-(μ-Ch)2-M'CN]^2- (M = Mo, W; Ch = S, Se; M' = Cu, Ag) have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M'→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M'CN as well as those of μ-Ch→M and M'→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M'CN make larger contributions to the hyperpolarizability, especially to γ.
基金the National Natural Science Foundation of China(Grant no.22078022).
文摘Proton conducting solid oxide fuel cell(H-SOFC)is an emerging energy conversion device,with lower activation energy and higher energy utilization efficiency.However,the deficiency of highly active cathode materials still remains a major challenge for the development of H-SOFC.Therefore,in this work,K_(2)NiF_(4)-type cathode materials Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ)(x=0,0.1,0.2,0.3),single-phase tripleconducting(e-/O^(2-)/H^(+))oxides,are prepared for intermediate temperature H-SOFCs and exhibit good oxygen reduction reaction activity.The investigation demonstrates that doping Ba into Pr_(2-x)BaxNi_(0.6)Cu_(0.4)O_(4+δ) can increase its electrochemical performance through enhancing electrical conductivity,oxygen vacancy concentration and proton conductivity.EIS tests are carried at 750℃ and the minimum polarization impedances are obtained when x=0.2,which are 0.068 Ω·cm^(2) in air and 1.336 Ω·cm^(2) in wet argon,respectively.The peak power density of the cell with Pr_(1.8)Ba_(0.2)Ni_(0.6)Cu_(0.4)O_(4+δ) cathode is 298 mW·cm^(-2) at 750℃ in air with humidified hydrogen as fuel.Based on the above results,Ba-doped Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ) can be a good candidate material for SOFC cathode applications.
基金Funded by the National Natural Science Foundations of China(Nos.51161015,51371094)Natural Science Foundation of Inner Mongolia,China(No.2011ZD10)
文摘The element Ni in the Mg2Ni alloy is partially substituted by M(M = Cu, Co, Mn) in order to ameliorate the electrochemical hydrogen storage performances of Mg2Ni-type electrode alloys. The nanocrystalline and amorphous Mg20Ni10-xMx(M = None, Cu, Co, Mn; x = 0-4) alloys were prepared by melt spinning. The effects of the M(M = Cu, Co, Mn) content on the structures and electrochemical hydrogen storage characteristics of the as-cast and spun alloys were comparatively studied. The analyses by XRD, SEM and HRTEM reveal that all the as-cast alloys have a major phase of Mg2Ni but the M(M = Co, Mn) substitution brings on the formation of some secondary phases, MgCo2 and Mg for the(M = Co) alloy, and Mn Ni and Mg for the(M = Mn) alloy. Besides, the as-spun(M = None, Cu) alloys display an entirely nanocrystalline structure, whereas the as-spun(M = Co, Mn) alloys hold a nanocrystalline/amorphous structure, suggesting that the substitution of M(M = Co, Mn) for Ni facilitates the glass formation in the Mg2Ni-type alloys. The electrochemical measurements indicate that the variation of M(M = Cu, Co, Mn) content engenders an obvious effect on the electrochemical performances of the as-cast and spun alloys. To be specific, the cyclic stabilities of the alloys augment monotonously with increasing M(M = Cu, Co, Mn) content, and the capacity retaining rate(S20) is in an order of(M = Cu) 〉(M = Co) 〉(M = Mn) 〉(M = None) for x≤1 but changes to(M = Co) 〉(M = Mn) 〉(M = Cu) 〉(M = None) for x≥2. The discharge capacities of the as-cast and spun alloys always grow with the rising of M(M = Co, Mn) content but first mount up and then go down with increasing M(M = Cu) content. Whatever the M content is, the discharge capacities are in sequence:(M = Co) 〉(M = Mn) 〉(M = Cu) 〉(M = None). The high rate discharge abilities(HRDs) of all the alloys grow clearly with rising M(M = Cu, Co) content except for(M = Mn) alloy, whose HRD has a maximum value with varying M(M = Mn) content. Furthermore, for the as-cast alloys, the HRD is in order of(M = Co) 〉(M = Mn) 〉(M = Cu) 〉(M = None), while for the as-spun(20 m·s^-1) alloys, it changes from(M = Co) 〉(M = Mn) 〉(M = Cu) 〉(M = None) for x = 1 to(M = Cu) 〉(M = Co) 〉(M = None) 〉(M = Mn) for x = 4.